物理化学学报 >> 2019, Vol. 35 >> Issue (10): 1112-1118.doi: 10.3866/PKU.WHXB201805032

所属专题: 二维材料及器件

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生物质羟基磷灰石作为模板制备三维石墨烯

王可心1,史刘嵘1,王铭展1,杨皓2,刘忠范1,3,*(),彭海琳1,3,*()   

  1. 1 北京大学化学与分子工程学院,分子动态与稳态结构国家重点实验室,北京分子科学国家实验室,纳米化学研究中心,北京 100871
    2 北京大学前沿交叉学科研究院,北京 100871
    3 北京石墨烯研究院,北京 100095
  • 收稿日期:2018-05-14 发布日期:2018-06-26
  • 通讯作者: 刘忠范,彭海琳 E-mail:zfliu@pku.edu.cn;hlpeng@pku.edu.cn
  • 基金资助:
    北京市科学技术委员会(Z161100002116002);北京市科学技术委员会(Z161100002116002, Z161100002116021);国家重点基础研究发展计划(973)项目(2014CB932500);国家重点基础研究发展计划(973)项目(2016YFA0200101);国家自然科学基金(21525310);国家自然科学基金(51432002);国家自然科学基金(51520105003)

Biomass Hydroxyapatite-templated Synthesis of 3D Graphene

Kexin WANG1,Liurong SHI1,Mingzhan WANG1,Hao YANG2,Zhongfan LIU1,3,*(),Hailin PENG1,3,*()   

  1. 1 Center for Nanochemistry (CNC), Beijing National Laboratory for Molecular Sciences, State Key Laboratory for Structural Chemistry of Unstable and Stable Species, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China
    2 Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, P. R. China
    3 Beijing Graphene Institute (BGI), Beijing 100095, P. R. China
  • Received:2018-05-14 Published:2018-06-26
  • Contact: Zhongfan LIU,Hailin PENG E-mail:zfliu@pku.edu.cn;hlpeng@pku.edu.cn
  • Supported by:
    the Beijing Municipal Science & Technology Commission, China(Z161100002116002);the Beijing Municipal Science & Technology Commission, China(Z161100002116002, Z161100002116021);the National Basic Research Program of China(2014CB932500);the National Basic Research Program of China(2016YFA0200101);the National Natural Science Foundation of China(21525310);the National Natural Science Foundation of China(51432002);the National Natural Science Foundation of China(51520105003)

摘要:

三维石墨烯(3DG)被广泛研究用于能量存储和转换器件中的导电框架材料。化学气相沉积(CVD)是制备品质三维石墨烯的重要方法,其中选择合适的模板材料对于调控石墨烯形貌和成本至关重要。在此,本文使用牛骨灰这一廉价易得的生物废弃物作为CVD模板,制备了高品质三维石墨烯。这种三维石墨烯表现出“双连续”的微观结构,即石墨烯框架及其空隙均是连续的,因而可以作为导电框架材料用于电化学储能器件。我们将硫均匀负载于三维石墨烯作为高性能锂-硫电池的正极材料,其在高倍率(2C)下具有约550 mAh·g-1的高比容量。此外,将牛骨灰模板蚀刻后所得溶液可作为原料用于磷酸生产,实现了高的原子利用率。这一工作将石墨烯制备与成熟的磷化工产业结合,发展了一种低成本、高原子经济性地制备三维石墨烯的新途径。

关键词: 三维石墨烯, 化学气相沉积, 生物废弃物, 羟基磷灰石, 锂-硫电池

Abstract:

As a new 2D material with excellent chemical stability, good electric conductivity, and high specific surface area, graphene has been widely used in energy storage and conversion devices. However, 2D graphene layers are easily stacked, which may significantly reduce the surface area and degrade the excellent electrical properties of graphene. To avoid this, one of the most effective methods is to construct 3D graphene (3DG) with specific porous microstructures. Chemical vapor deposition (CVD) is an important method for the synthesis of high-quality 3DG, where templates play a defining role in controlling the structure and cost of 3DG. Metallic materials with 3D microstructures, such as nickel foam, have proven to be useful as substrates for the growth of high-quality 3DG. However, metal substrates are usually expensive, and the pickling solution generated after etching may cause environmental problems. Therefore, non-metallic substrate materials with lower costs have been investigated for the preparation of 3DG. Herein, we developed a novel template material, mammal bone ashes, for the CVD preparation of 3DG. Mammal bone ash is an inexpensive and abundant biomass hydroxyapatite. During the high-temperature CVD reaction, the bone ash powders were slightly sintered to form a continuous porous structure with graphene coating. The morphology of 3DG is inherited from the microstructure of bone ash templates. After removing the bone ash template with hydrochloric acid, the template-grown 3DG was obtained with a unique bicontinuous structure, i.e. both the graphene framework and the void space were continuous. In addition, the pickling solution of the bone ash templates after etching was exactly the same as that for the raw materials for the production of phosphoric acid to achieve high atom utilization. We further optimized the graphitization degrees, layer number, and porous morphology of 3DGs. The microstructure evolution of 3DG is highly relevant to the layer thickness and uniformity of graphene layers. A short growth time would lead to a non-uniform and thin layer of graphene, which is not able to support a complex 3D porous structure. In contrast, a uniform graphene layer with proper thickness is capable of forming a robust 3D architecture. In addition, the facile CVD method can be extended to a series of metal phosphate templates, including tricalcium phosphate [Ca3(PO4)2], trimagnesium phosphate [Mg3(PO4)2], and aluminum phosphate [AlPO4]. 3DG with bicontinuous morphology is promising as a conductive frame material in electrochemical energy storage devices. As an illustration, high-performance Li-S batteries were fabricated by the uniform composition of an S cathode on 3DG. In comparison with heavily stacked 2D graphene sheets in reduced graphene oxide / S composite, the non-flat structure of 3DGs remained unchanged even after the harsh melt-diffusion process of high-viscosity liquid sulfur. The resulting 3DG/S cathode delivered a high specific capacity of ~550 mAh∙g-1 at a high current rate (2C). Our work opens an avenue to the low-cost and high-utility production of 3D graphene, which could be integrated with the well-developed phosphorus chemical industry.

10.3866/PKU.WHXB201809013.F009  

Key words: 3D graphene, Chemical vapor deposition, Bio-waste, Hydroxyapatite, Li-S battery

MSC2000: 

  • O646